Treatment of hydrocarbon oils



Feb. 26, 1935.

FURNACE 23) G. EGLOFF TREATMENT OF HYDROCARBON OILS Filed May 14, 1931 FRACTIONATOR TOPPING AND FRACTIONATING COLUMN INVENTOR GUSTAV EG LOFF which contains a substantial proportion of relaing high anti-knock value as well as other desir- 15 1 components, collecting the unvaporized, oil, toand/or other relatively light components of a 20 35 vapors which may be condensed in said iractionoil, preferably containing a substantial propor- 35 Patented Feb.26,-1935 'I j I I I I A UNITED. STATES PATENT OFFICE TREATMENT OF HYDROCABBON OILS Gustav Eglofl, Chicago, 111., assignor to Universal Oil Products Company, Chicago, 111., a corporation of South Dakota Application May 14, 1931, Serial No., 537,258

7 Claims. (01. 196-60) This invention relates to the treatment of hyand/or liquidswithin the cracking system by indrocarbon oils and refers particularly to the condirect heat exchange therewith. version of hydrocarbon oils into oils of more de- The process of the present inventiontis best sirable characteristics. adapted to the treatment of crude oils which 5 The primary concepts of the present invention contain a substantial proportion of gasoline of 5 comprise separating the relatively light and relainferior quality, especially with respect to its tively heavy components of crude petroleum, anti-knock rating, as, by the provisions of the thence subjecting each of. the separate compresent invention, this inferior motor fuel may ponents to independently controlled conversion be separated from the heavier portions of the 10 conditions for the production of substantial quancrude and thence subjected to conditions, prefer- 10 titles of more desirable products such as motor ably of relatively high temperature and substaniuel of high anti-knock value. tial super-atmospheric pressure, under which it I In its more specific embodiment, the invention will be reformed or its characteristics will be so may comprise subjecting a crude oil, of the type altered that the product is a motor fuel possesstively light components such as gasoline or other able characteristics. r

low boiling distillates, to substantial vaporization, The present invention possesses the economic subjecting the vapors to fractionation to effect advantage of eifecting the reconversion or alterseparation and recovery of said relatively light ing the undesirable properties of the gasoline gether with reflux condensate from said fraccrude oil simultaneously with and in a portion tionation, and subjecting this oil, which comprises of the same apparatus in which the relatively relatively heavy components of the crude, to conheavy components of said crude oil are converted I version conditions in the heating element, preierinto more desirable light products, accomplishing ably under a substantial superatmospheric presthe temperature treatment of each of the two 25 sure, introducing the heated products into a reaccomponents of the crude under independently tion zone, withdrawingboth vaporous and liquid controlled conditions which give the most'desirproducts from said reaction zone to a vaporizing able results from each oil. zone preferably maintained under substantially The attached diagrammatic drawing illustrates reduced pressure and wherein vaporous products one form ofapparatus which embodies the prin- 30 may separate from the residual products of conciples of the present invention and the following version, subjecting the vaporous reaction proddescription of the drawing embraces a descripucts to fractionation, returning the relatively tion of the process Of the invention as it may be heavy insufiiciently converted components of the practiced in'the apparatus illustrated. A crude ating zone to further'conversion in said heating tion of relatively light components, such as motor elementfsubjecting the vapors and gases from fuel of inferior quality, may be supplied through said fractionator to condensation and cooling and i d ve 2 to p p 3 from which it y collecting the resulting products, simultaneously fed through line a ve at exchanger Subjeetingth-e 1 t 1 light components of the line '7, valve 8, heat exchanger 9, line 10, valve 11, 40 crude oil separated from the relatively heavy com-'- hfeat exchanger 2, }6 13 and valve 14 in o t ponents, as already described, to independently pmg and fractlona'tmg column Heat controlled conversion conditions in a separate 32:25:;f fiz gi gg g lxggfig 23 5222 2:

v exchanger 9 may be located in the path oi liquid Sublected therem and m subsequently subJectmg and va orous roducts assin from th r portions of the system to the same treatment as p p p g e eactmn chamber. to the vaporizing zone. Heat exchanger that afiorded the heated'products m the first 12 may be located within the path of heated oil mentioned heating element passing from the secondary heating element to 50 Asa feature of the invention, a portion or all of the reaction chamber of t cracking system v the heat required for efiecting' substantial vapori- The crude oil y be heated n a t exchanger zation of the crude oil to permit separation of its by indirect contact with the relatively hot prodlighter from its heavier components may be reucts within the cracking system. It will be uncoveredfrom the relatively hot vapors and gases derstood that heat exchangers located elsewhere 5 in the system or other means of supplying heat I to the crude oil may be employed, if desired. It

will also be understood that any or all of the heat exchangers mentioned may be by-passed, if so desired, by well known means, not illustrated in the drawing.

Topping and fractionating column 15 may be maintained under substantially atmospheric or under a substantial super-atmospheric pressure, or, if desired, subatmospheric pressures may be employed in this zone. The crude oil may be heated under substantially the same or under a higher pressure than that employed in column 15 and the temperature attained by the crude, prior to its introduction to this column, is suf ficient to effect vaporization of a substantial portion of the oil under the conditions maintained in. column 15. The portion vaporized includes substantially all of the light components of the crude which it is desired to separate from the heavier components. Fractionation of the V2, pore and separation of said relatively light components therefrom may be effected by any suitable fractionating means such as bubble trays, perforated pans, packing or the like in column 15.

The relatively heavy components of the crude oil, including those remaining unvaporized in col umn l5 and the reflux condensate condensed from the vapors in this zone, may be withdrawn from the lower portion thereof through line l6 and valve 1'?! to pump 18 from which they may be fed through line 19, valve 20 and line 21 to heating element 22.

Heating element 22 maybe located within any suitable form of furnace 23, capable of supplying the required heat to the oil undergoing treatment in the heating element. The oil is heated in this zone to the desired conversion temperature preferably under a substantial super-atmospheric pressure and maybe discharged "from the heating element through line 24, valve 25 and line 26 into reaction chamber 27. Chamber 27 is also preferably maintained under a substantialsuper-atmospheric pressure which may be substantially equalized with or lower than that employed in the heating element. Both liquid and vaporous products may be simultaneously discharged from chamber 27 through line 28, valve 29, heat exchanger 9 and line 30 into vaporizing chamber 31 which is preferably maintained under a substantially reduced pressure relative to that employed in chamber 27.

The vaporous products may separate from the residual products of conversion in chamber 31. In case the residual material produced is a liquid it may be withdrawn from chamber 31 through line 32 and valve 33 to storage or to any desired further treatment, however, if so desired, conditions may be so regulated in chamber 31 that a substantially dry carbonaceous residual product will result, in which case it may be allowed to accumulate withinthe chamber to be removed after the operation of the process is discontinued. Or, if desired, a plurality of chambers similar to chamber 31, but not illustrated in the drawing, may be employed and may be operated either alternately or simultaneously to prolong the operating cycle.

Vapors and gases may be withdrawn from chamber 31 through line 34, valve 35, heat exchanger 6 and line 36 to fractionation in fractionator 37. The relatively heavy insufliciently converted components of the vapors may be condensed within the fractionator collecting within neeaaee the lower portion thereof from which they may bewithdrawn through line 38 and valve 39 to pump 40, by means of which they may be fed through line 21 and valve 1 to heating element 22 for further conversion, together with the topped crude from column 15. Fractionawd vapors and gases may pass from iractionator 37,

through line 42 and valve 43, may be subjected to condensation and cooling in condenser as, products from which may pass through line 45 and valve 46 to be collected in receiver i7. Un condensable gas may be released from receiver d7 through line 48 and valve 49. Distillate may be withdrawn from. the receiver through line and valve 51. receiver 47 may, if desired, be recirculated by well known means, not illustrated in the draw-= ing, to the upper portion of fractionator 3? to assist fractionation of the vapors in this zone.

The relatively light components of the crude oil which are separated from its heavier com ponents in column may be separated in this same zone into a relatively light distillate and uncondensable gas. The distillate, which preferably ccmprises substantially all of the naturally contained gasoline in the crude, may collect upon a tray or deck, not shown, in the upper portion of column 15 to be withdrawn therefrom through line '70 and valve 52 to pump 53 by means of which it may be supplied through line 54 and valve 55 to heating element 56. The uncondensable gas, withdrawn from column 15 above the point from which the gasoline or relatively light distillate is withdrawn, may pass through line 5'? and. valve 58 to pump 59, which may function as a vacuum pump in case subatmosploeric pressure is maintained in column 15. The uncon densable gas may be passed from pump 59 through line 60 and may be discharged, all or in part, from the system to storage or elsewhere through line 61 and valve 62 or may be discharged, all or in part, .from'line 60 through line 63 and valve 64 into line 54 and thence to heating element 56, together with the distillate with drawn from column 15.

Heating element 56 may be located within any suitable furnace 65 and the distillate or distillate and gas supplied thereto may be heated to the desired temperature under any desired pressure conditions and'preferably under a substantial super-atmospheric pressure. The heated materials may be discharged from heating element 56 through line 66, valve 67, heat exchanger 12, line 68 and valve 69 into line 26 commingling therein with the heated oil discharged from heating element 22 and passing therewith to reaction chamber 27 to undergo, in this chamber and in subsequent portions of, the system, the same treatment, as already described, to which said heated oil from heating element 22 is subjected.

Pressures employed within the system may range from sub-atmospheric to super-atmospheric pressures as high as 2000 pounds or more per square inch. Conversion conditions employed may-range from 800 to 1200 F., more or less. Preferably, the topped crude and reflux condensate is subjected in the heating element in which they are treated to temperatures of the order of 850 to 950 F., and superatmospheric pressures which may range from 100 to 500 pounds per square inch, more or less. Preferably reduced pressures of the order of substantially atmospheric to 100 pounds per square inch or thereabouts are employed in the vaporizing, fraction- A portion of the distillate tirom i ating, condensing and collecting portions of the 76 cracking system. Pressures employed in the topping and fractionating column may range from sub-atmospheric to 100 pounds or more superatmospheric pressure per square inch. The rela-- tively light components of the crude may be subjected in the heating element in which they are treated to temperatures of the order of 900 to 1200 F., more or less, under pressure conditions which may range from sub-atmospheric to 500 pounds per square inch, or more super-atmospheric pressure.

As an example of one of the many operations which may be practiced in the process of the present invention, a Pennsylvania. crude oil containing approximately 37% of gasoline is the raw oil charging stock supplied to the process. Substantially all of the gasoline is separated from the crude in the topping and fractionating colunm and after subjection to a temperature of 7 approximately 940 F. under a pressure of approximately 400 pounds per square inch is introduced into the reaction chamber of the cracking system together with the topped crude which is previously subjected, together with the reflux condensate from the cracking system, to a temperature of about 900 F. under a super-atmospheric pressure of approximately 350 pounds per square inch. A pressure of about 350 pounds per square inch is maintained in the reaction cham ber but is reduced in the vaporizing, fractionating, condensing and collecting portions of the system to a substantially equalized pressure of about 50 pounds per square inch. This operation may yield approximately 72% of motor fuel based on the crude oil charged to the system. This motor fuel may have an octane numberof about 83 as compared with an octane number of about 20 for the straight run gasoline obtained from the crude before it is reformed. In addition, to the motor fuel about 18% of heavy residual oil and a relatively small percentage of coke or carbonaceous material are produced, the only other product of the system being a rich uncon densable gas.

I claim as my invention:

1. A process of hydrocarbon oil conversion, which comprises subjecting a crude oil containing gasoline to a distillation temperature sufllcient to vaporize the gasoline, separating the gasoline from the topped crude and subjecting same to vapor phase cracking conditions, simultaneously subjecting the topped crude to liquid phase cracking conditions of temperature and superatmospheric pressure in a separate zone, merging the highly heated vapors from the vapor phase cracking zone with the heated topped crude issuing from the liquid phase cracking zone, discharging said mixture into an enlarged reaction zone where separation takes place between vapors and non-vaporous residue, subjectingthe vapors to fractionation to condense the heavier fractions thereof as reflux condensate, removing the vapors remaining uncondensed after fractionation and condensing and collecting same as a distillate product of the process.

2. A process such as claimed in claim. 1, characterized in that the gasoline passmg through the vapor phase cracking zone subjected to higher tempera ure: conditions than the topped crude passing through the liquid phase cracking zone.

3. A process such as claimed in claim 1, characterizad in that the crude ineiuoling gasoline is raised to distillation temperature by indirect heat exchange with the products issuing from the vapor phase and liquid phase cracking zones.

A such as claimed in claim 1, characmrized in that the conditions of vapor phase cracking are controlled to substantially increase the anti-knock characteristics of the gasoline subjected to vapor phase cracking.

5. A process of hydrocarbon oil conversion, which comprises subjecting a crude oil containing gasoline to a distillation temperature sufficient to vaporize the gasoline, separating the gasoline from the topped crude and subjecting same to vapor phase cracking conditions, simultaneously subjecting the topped crude to liquid phase cracking conditions of temperature and superatmos pheric pressure in a separate zone, merging the highly heated vapors from the vapor phase cracking zone with the heated topped crude issuing from the liquid phase cracking zone, discharging said mixture into an enlarged reaction zone where separation takes place between vapors and nonvaporous residue, subjecting the vapors to fractionation to condense the heavier fractions thereof as. reflux condensate, returning regulated portions of the reflux condensate to the liquid phase cracking zone for retreatment, removing the vapors remaining uncondensed after fractionation and condensing and collecting same as a distillate product of the process.

6. A process of hydrocarbon oil conversion which comprises subjecting a crude oil containing gasoline to distillation temperature suflicient to vaporize the gasoline and separating the gasoline from the crude, passing portions of the crude heavier than gasoline through a heating zone and heating the same therein to cracking temperature under suiflcient pressure to maintain a substantial portion thereof in liquid phase, simultaneously subjecting gasoline boiling hydrocarbons separated from the crude, while substantially in vapor phase. to higher cracking temperature than the oil in said heating zone and then commingling the same with the heated products discharged from said heating zone, separating the commingled oils in an enlarged separating zone into vapors and residue, fractionating the separated vapors to condense heavier fractions thereof, and finally condensing and collecting the vapors uncondensed by the fractionation.

t. A process of hydrocarbon oil conversion which comprises subjecting a crude oil containing gasoline to distillation temperature sufhcient to vaporize the gasoline and separating the gaso line from the crude., passing portions of the crude heavier than gasoline through a heating zone and; heating the same therein to cracking tempera-= ture under pressure, simultaneously passing gasoline boiling hydrocarbons separated from the crude through a second heating zone maintained at higher cracking temperature than the firstnamed heating zone and heating the same therein sufliciently to enhance the anti-knock vaiue thereof, ccmmingling the heated products from said heating zones and separating the same in an enlarged separating zone into vapors and residue, and fractionating and condensing the separated vapors.

GUSTAV EGLOFF. 

